Process for preparing a hydrogenation catalysts

ABSTRACT

Copper compositions that are useful as hydrogenation catalysts are disclosed. In particular, the copper compounds are catalysts for the selective hydrogenation of oils that contain unsaturated fatty acyl components such as unsaturated vegetable oils. Methods of preparing the copper compositions are also disclosed. Methods of hydrogenating unsaturated compositions that contain at least two sites of unsaturation using the hydrogenation catalysts, along with products obtained from the hydrogenation reactions described herein are also disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.60/674,707, filed Apr. 26, 2005, which is incorporated by referenceherein in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is directed to copper catalysts useful forhydrogenating unsaturated compositions, methods of preparing thecatalysts, methods of hydrogenating unsaturated compositions and thehydrogenated products obtained therefrom.

2. Background of the Invention

The hydrogenation of unsaturated substrates is a technology widely usedfor obtaining products which can be used in various fields, from thefood industry to the field of plastic materials and the like. Severalmethods are known for hydrogenation (a chemical reduction by means ofadding hydrogen across a double bond), most of which use gaseoushydrogen in the presence of a suitable catalyst. The latter normallycomprises a transition metal, usually a metal of group 10 of theperiodic table, i.e., Ni, Pd or Pt. If these are present as impuritiesin the hydrogenated substrate, they can cause oxidation or toxicologicalproblems in the case of food. Hydrogenation catalysts based on othertransition metals having fewer drawbacks than those listed above arealso known, but these also have a lower catalytic activity.

Hydrogenation of plant oils removes or reduces the amount of componentsin the oil responsible for offensive odors, poor taste and poorstability. Thus, hydrogenation provides plant oils that are useful ascomponents for many nutritional products such as nutraceuticals andfood, and for food preparation such as frying oils.

Soybean (i.e., Glycine max L. Merr.) seeds are recognized to representone of the most important oilseed crops presently being grown in theworld. Such seeds provide an excellent source of vegetable oil. Whilesoybean oil represents an important worldwide food source, flavor andoxidative stability problems associated with its customary fatty acidcomposition reduces its attractiveness in some applications.

Oxidative stability relates to how easily components of an oil oxidizewhich creates off-flavors in the oil, and is measured by instrumentalanalysis such as Oil Stability Index or Accelerated Oxygen Method (AOM).The degree of oxidative stability is rated as the number of hours toreach a peroxide value of 100.

Soybean oil contains five different fatty acids (in the form of fattyacid acylglycerol esters) as its major components. These five fattyacids are: palmitic acid (C16:0) which averages about 11 percent byweight; stearic acid (C18:0) which averages about 4 percent by weight;oleic acid (C18:1) which averages about 20 percent by weight; linoleicacid (C18:2) which averages about 57 percent by weight; and linolenicacid (C18:3) which averages about 8 percent by weight of the total fattyacids. The stability problem which influences the flavor of soybean oilhas been attributed to the oxidation of its fatty acids, andparticularly to the oxidation of the linolenic acid (C18:3) component.

Oxidized fatty acids decompose to form volatile flavor-impartingcompounds. The relative order of sensitivity to oxidation islinolenic>linoleic>oleic>saturates. Linolenic acid has been known to bethe primary precursor for undesirable odor and flavor development. Sincecommodity soybean oil currently marketed today contains relatively highamounts of linolenic acid (7-10%) compared to other food oils such ascorn oil which has about 1%, its use is constricted unless it has beenhydrogenated. As a general rule the linolenic acid content should bebelow 1-2% in order to have the widest food application and to qualifyfor rigorous use environments such as for frying oils.

Soybean oil suffers from a lack of stability for frying applications dueto its relatively high concentration of linolenic acid of 7 to 10%. Thiscauses the oil to oxidize rapidly and generate off flavors and alsocauses early breakdown in the frying applications, resulting inpremature foaming and darkening. Frying stability can be enhanced if thelinolenic acid concentration can be reduced.

To address the flavor and stability problems of soybean oil due to thelinolenic acid content, various processing approaches have beenproposed. Such processing of the soybean vegetable oil includes: (1)minimizing the ability of the fatty acids to undergo oxidation by addingmetal chelating agents, antioxidants, or packaging in the absence ofoxygen; or (2) the elimination of the endogenous linolenic acid byselective hydrogenation. These approaches have not been entirelysatisfactory. The additional processing is expensive, time consuming,commonly ineffective, and frequently generates undesirable by-products.While selective hydrogenation to reduce the linolenic acid content mayimprove oil stability somewhat, this also generates positional andgeometric isomers of the unsaturated fatty acids that are not present inthe natural soybean oil.

Hydrogenation can be used to improve performance attributes by loweringthe amount of linolenic and linoleic acids in the oil. In this processthe oil increases in saturated and trans fatty acids, both undesirablewhen considering health implications. In many instances, the increase intrans fatty acids is proportional to the amount of linolenic acid in thestarting oil.

Due to increased knowledge of the behavior of trans fats, i.e. transfatty acid esters, in the human body and concerns of their contributingto coronary heart disease, it is recommended that the intake of transfats be reduced. Research has shown that diets high in saturated fatsincrease low density lipoproteins, which promote the deposition ofcholesterol on blood vessels. More recently, dietary consumption offoods high in trans fatty acids have also been linked to a lowering ofhigh density lipoprotein relative to low density lipoprotein and tocause an increase in inflammation. In the United States, food companiesare required to label the trans content of their products above athreshold level. This has added impetus to lower the amount of transfats in foods, particularly foods relatively high in oil, such as friedfoods, including potato chips, etc. However, hydrogenation remains theprimary option to convert an unstable oil to a stable oil.

Thus, polyunsaturated oils are hydrogenated to reduce the degree ofunsaturation in the oil, prior to subsequent processing to obtainsecondary products, such as food grade oils, additives, lubricants andthe like. The content of linolenic acid (C18:3) in the oil is reduced byhydrogenation to a more saturated oil, containing increased amounts ofthe monoene (C18:1) and diene (C18:2).

Reduction of the double bond content in polyunsaturated oils istraditionally carried out by partial hydrogenation, catalyzed by atransition metal catalyst. Various transition metals, such as nickel,palladium and platinum have been used as hydrogenation catalysts.Catalysts vary in degree of selectivity. The selectivity referred to inthis context is the ability of preferentially reducing linolenic acidbefore linoleic acid and oleic acid. Selectivity in this context alsoapplies to the ability of a catalyst to reduce by hydrogenating only toform monoenes, without reducing to full saturation. Precious metalcatalysts are generally the most active and also the least selective.They typically produce high amounts of saturated fatty acids for aminimal reduction of linolenic acid. Nickel catalysts are more selectiveand have a greater preference for reducing linolenic acid to monoenewhile producing less saturates. However, copper-chromium combinationcatalysts (i.e., copper chromite catalyst) have hitherto been found tobe the most selective for production of the monoene. The hydrogenationof the polyunsaturated oils with copper chromite can produce thecorresponding monoene, with little or no production of the saturatedfatty acid.

Nickel catalyzed hydrogenation uses small amounts of catalyst forrelatively short periods of time to reduce the linolenic acid content tothe desired range, which is often 1.5%. The oil may then additionally bewinterized (chilled and cold filtered) to remove any crystallinefractions. A problem with the hydrogenation processes of today is thatdouble bonds in fatty acids can also isomerize to form trans fatty acidsduring hydrogenation, many of which are rare in nature. Some of theseare trans fatty acids. When nickel catalysts are used, saturated andtrans fatty acids are produced in high amounts relative to the desiredamount of reduction of linolenic acid. This is because nickel catalystssuffer from a lack of optimum selectivity. As a result, the trans fattyacid content of oils hydrogenated with nickel catalysts can be higherthan 10%.

Hydrogenation conditions to minimize trans isomer formation whilereducing the oxidatively unstable species in edible oil, such as thepolyunsaturated acids linolenic and linoleic acid, are currently beingstudied by many in the industry. Those catalysts currently beingexamined are generally precious metal based, and hydrogenation iscarried out under extremely mild conditions, such as low temperatures.However, to date this has only resulted in a minimal decrease in transfatty acid content in hydrogenated oils, at the cost of increasedsaturated fatty acid content and the use of very expensive catalysts.

Precious metal catalysts can be poisoned from various minor componentsin oils. As a result activity is lost over time and reaction conditionsmust be continually monitored and altered. These catalysts may beemployed in column reactors which require emptying and recharging afterthe useful catalyst life has ended. The catalyst then must be returnedto the catalyst company for credit and regeneration. All of thisinvolves catalyst loss and added cost for column recycling. As preciousmetal catalysts lose activity and must be recovered, users of preciousmetal catalysts are often required to purchase a large excess ofprecious metal to form a “pool” or “kitty” of precious metal, so thatthe catalyst producer can provide fresh catalyst as needed. As a result,the use of precious metal catalysts is accompanied by a very largecapital investment in precious metals.

Selective hydrogenation for producing oils for frying applications usingcopper chromite catalyst has been known since at least the late 1960's.Vegetable oils have been selectively hydrogenated to decrease thelinolenic acid content without increasing the saturated fatty acidcontent constant and only minimally decreasing the linoleic acid contentin soybean oil. The trans content was of no concern in those days asthis was prior to the discovery of the detrimental effects of theseisomers to human health. Selectively hydrogenating soybean oils producedoil with less than 2% linolenic acid and improved frying stability.However, copper chromite has low catalytic activity and requires verylong reaction times. Thus reactor time is measured in hours, not inminutes, adding to increased production costs over comparable nickelcatalyzed reactions.

Further, copper chromite suffers from the problem that chromium is oneof the components of the catalyst, and thus any plant using thiscatalyst must handle the recycling and disposal of chromium in asatisfactory manner. First, the catalyst must be recovered from the oilafter the hydrogenation reaction by suitable means, such as bycentrifugation or filtering. Traces of catalyst remaining in the oilmust be removed in a thorough manner, such as filtering throughbleaching earth. This removal generates significant quantities of solidwaste containing spent copper chromite catalyst and would requireshipment to a land fill or to a possible reclamation facility. Inaddition, the finely powdered catalyst containing chromium could pose asignificant health risk to workers operating the processes.

Filtered oil further requires washing with a suitable solution ofchelating agent to further recover chromium. This wash water wouldrequire passage through expensive ion exchange resin columns to reducethe chromium concentration in the water prior to discharge in order toachieve allowable limits. Further, regulatory permits to allow dischargeof trace levels of chromium in waste water must be obtained. In order tomeasure chromium released to the environment, expensive analyticalmonitoring equipment and trained operators would be required. Becausethe use of copper chromite was not attractive for the above reasons, itscommercial use as a hydrogenation catalyst is obsolete.

Other copper based catalysts are known in the art. These catalysts havethe advantage of being non-chromium. However, they still have thedisadvantage of being no faster than copper chromite in reaction time.Furthermore, some were fabricated on a support, generally a molecularsieve, making them somewhat expensive to make. In addition, highhydrogenation temperatures were required (170 to 200° C.). To preparethese catalysts, a support material was slurried in a solution of copper(II) nitrate, and sodium carbonate was added to precipitate copper (II)carbonate onto the support. This preparation was then heated to 350° C.for two hours.

Genetic varieties of soybeans containing oil with low linolenic acidrequired for frying have just begun to be commercialized. The mostrecent variety to be commercialized has utilized a traditional geneticbreeding program for its development. In general, oils produced fromgenetic varieties are expensive alternatives to hydrogenated oils.

There is an evident need in the fats and oils industry for an economicalcatalyst for soybean oil hydrogenation which selectively reduceslinolenic acid without generation of significant levels of trans fattyacids or formation of saturated fatty acids.

BRIEF SUMMARY OF THE INVENTION

The copper compositions disclosed herein are useful as hydrogenationcatalysts. In particular, the copper compositions are catalysts for theselective hydrogenation of oils that contain unsaturated fatty acylcomponents. The present invention is also directed to a method ofpreparing the copper compositions that are useful as hydrogenationcatalysts. The present invention is further directed to a method ofhydrogenating compositions containing at least two sites ofunsaturation. The present invention is also directed to the productsobtained from the hydrogenation reactions described herein.

DETAILED DESCRIPTION OF THE INVENTION

In embodiments of the invention, the present invention is directed toprocesses of hydrogenating a composition containing at least two sitesof unsaturation. The processes comprise: a) preparing a mixture bycontacting the composition with a hydrogenation catalyst comprising atleast one of the following materials: heat-treated copper metal,chemically and optionally heat-treated copper hydroxide, heat orchemically treated copper carbonate/copper hydroxide, and a malachitematerial; and b) heating the mixture at a temperature from about 50° C.to about 250° C. under a hydrogen atmosphere; where the composition ishydrogenated.

In all aspects of the present invention, the temperature, temperaturesor ranges represent the temperature at which the step is conducted.However, the temperature can be more than one temperature in the givenrange because of fluctuations in temperature during the step.

In an embodiment, the temperature for step b) can be any temperature(s)from about 50° C. to about 250° C. In other embodiments, the temperatureis from about 100° C. to about 250° C., or from about 100° C. to about200° C., or from about 160° C. to about 200° C., or from about 140° C.to about 220° C. Illustratively the temperature is about 160° C., about180° C., or about 200° C.

The term “hydrogenation” is well-known in the art, and the term“hydrogen atmosphere” is known to mean that the atmosphere in contactwith the unsaturated composition comprises hydrogen gas. The pressure ofhydrogen includes the range of about 5 psi to about 1000 psi. Inembodiments of the invention, the value is from about 20 psi to about150 psi, or from about 40 psi to about 80 psi.

The time for which the mixture is heated under a hydrogen atmosphere isdependent, inter alia, upon the catalyst of the invention that is usedand the desired properties of the resulting hydrogenated composition.For example, the time can range from about 1 minute to about 48 hours(for example, about 30 minutes to about 8 hours, or about 30 minutes toabout 4 hours).

Suitable compositions for the present method include any compositioncontaining at least two sites of unsaturation. Such compositions cancomprise a single compound or mixtures of compounds wherein at least onecompound contains at least two sites of unsaturation. The methoddescribed herein is useful for fully hydrogenating or partiallyhydrogenating the composition. As such, the terms “hydrogenation” or“hydrogenating” as used herein are intended to include partialhydrogenation.

Polyunsaturated fatty acyl compositions comprise compounds and mixturesthat contain compounds of the following generic structure:

wherein R is a carbon chain from about 2 to about 23 carbons andcontains at least two sites of unsaturation; A can be a residue of amonohydric alcohol, a diol, polyol, or glycerol, or a hydroxy, alkoxy oraryloxy moiety. The above general structure includes the followingsubstructure:

wherein R is as described above, and G¹ and G² are each independentlyselected from the group consisting of hydrogen and,

wherein Z represents a carbon chain from about 2 to about 23 carbons inlength, optionally having at least two sites of unsaturation. Thisformula encompasses the fatty acid esters commonly found in vegetableoils and polyunsaturated vegetable oils such as palmitic acid (C16:0);stearic acid (C18:0); oleic acid (C18:1); linoleic acid (C18:2); andlinolenic acid (C18:3).

Preferably, the fatty acyl composition containing at least two sites ofunsaturation is a vegetable, animal or synthetic fat or oil, orderivatives or mixtures thereof. References made herein to “fatty acids”are intended to mean fatty acids in the form of fatty acid esters in thefatty acyl composition, that is a vegetable, animal or synthetic fat oroil, or derivatives or mixtures thereof, unless the fatty acid isspecifically referred to as a “free fatty acid.” In this context, it ispreferred that the fatty acid or derivative thereof is a triglyceride,diglyceride or monoglyceride or alkyl ester containing a residue of thefatty acid.

References to levels of “fatty acids” in oils refer to the level offatty acid chains in the form of esters such as glycerides. For example,a fatty acyl containing composition comprising one or morepolyunsaturated (i.e. two or more sites of unsaturation) vegetable fattyacid(s) or derivatives or mixtures thereof can include the fatty acidscontained in oils in the form of fatty acid esters.

In the generic structure above, when A is a residue of glycerol, thenthe fatty acyl composition can comprise a triglyceride, diglycerideand/or monoglyceride of a fatty acid (i.e., glycerol alkanoates), andmixtures thereof. Such a diglyceride or triglyceride will have two orthree fatty acid chains, respectively, wherein at least one of thechains has at least two sites of unsaturation. More preferred mono-, di-and triglycerides include glycerides of vegetable oil fatty acids. Mostpreferably, such glycerides are naturally occurring in a vegetable oilstarting material.

In this preferred embodiment, the fatty acyl containing composition isan edible oil. Preferred edible oils include vegetable oils. Suitablevegetable oils include but are not limited to: soybean oil, linseed oil,sunflower oil, canola oil, rapeseed oil, cottonseed oil, peanut oil,safflower oil, derivatives and conjugated derivatives of said oils, andmixtures thereof. These oils are known as polyunsaturated vegetableoils. Most preferably, the oil is soybean oil.

The present invention can be used to prepare oils low in linolenic acidand lower in trans fatty acids than partially hydrogenated oils preparedby conventional processes, such as with nickel catalysts. The oils ofthe invention have good oxidative stability due to the lowered contentof linolenic acid.

Illustrative applications for use these oils include, but are notlimited to food and beverages, animal feed, technical applications,nutritional supplements, beverages, cosmetics and personal careproducts, and pharmaceuticals/nutraceuticals.

Illustrative food applications include frying fats and oils, margarineoil, spread oil, bakery fats, frozen dough, cookies with oil, creamcakes (foam cakes), yeast-raised cakes, bread products (bread, buns,rolls), fried bread (with antioxidants), confectionary products, icings,dairy products, cheese products, pasta products, shortening, fatmixtures, emulsions, spray oils, dressings, milk, non dairy proteinpowders, soups, dressings, meats, gravies, canned meats, meat analogues,bread improvers, beverages, energy drinks, snacks, desserts, ice creamand bars, colors, flavor mixes, emulsifier mixes, baby food, frozenfoods fat, spray oil for bakery applications; releasing agent oil forpans, belts, molds, and the like; incorporation into emulsions such assauces, creams, mayonnaise, toppings, yogurts, microwave popcorn fat,and antioxidants.

Illustrative feed applications include sources of high nutritional valuein feed for, for example, fish, shrimp, calves (as milk replacer), pigs,sows, piglets, companion animals, pets, mink, and poultry.

In addition, oils of the invention can be used as a starting materialfor derived processes and products, such as feedstock for lipidmodifications such as fractionation and chemical or enzymatictransesterification or interesterification reactions to prepare usefultriacylglycerols, diacylglycerols, monoacylglycerols, esters and waxes.The oils of the invention can also be blended with other oils or fats toprovide a blend having desired characteristics.

Derivatives of these oils include genetically modified oils. One desiredtrait of genetically modified oils is the lower content of linolenicacid compared to natural oils. Some low level varieties have linolenicacid levels as low as about 1.2 to about 1.6%. In natural varieties, thelevel of linolenic acid is generally about 7-10%. Low linolenic acidvarieties can benefit substantially by the hydrogenation method of thepresent invention especially when the level of linolenic acid is aboveabout 2%, but below the usual amount contained in the correspondingnatural variety. The present method will yield a hydrogenated orpartially hydrogenated vegetable oil that contains conjugated linolenicacid(s) (CLA), which are not present in the low-level varieties.

When applied to a vegetable oil the present method of hydrogenationadvantageously yields a hydrogenated or partially hydrogenated vegetableoil with desirable characteristics for use where liquid oils are needed,such as in foods and food preparation. The present method producesvegetable oils having a linolenic content of no greater than about 5%.The same product will also have a conjugated linolenic acid content ofno greater than about 1% and a trans fatty acid content of no greaterthan about 10%. More preferred vegetable oil products of the presentmethod have a linolenic acid content of no greater than about 3%, andmost preferably 1%. These more preferred vegetable oils can also have atrans fatty acid content of no greater than about 8%, and mostpreferably no greater than about 3% as well as a conjugated linolenicacid content no greater than about 1%.

Copper catalysts of the invention include heat-treated copper metal,chemically and optionally heat-treated copper hydroxide, and heat orchemically treated (e.g., hydrogen peroxide-treated) coppercarbonate/copper hydroxide (also referred to as basic copper carbonate)compositions. It has been found that the above copper compounds in theirneat condition do not catalyze the hydrogenation described herein to anappreciable degree, if at all, and that these compounds can be made morecatalytic by employing the methods of preparing a catalyst describedherein. In another embodiment, a hydrogenation catalyst used in thehydrogenation methods of the invention comprises a malachite material(including natural malachite mineral and synthetically preparedmalachite (e.g., a precipitated malachite)).

In various embodiments of the invention, the catalysts used in thehydrogenation methods of the invention (e.g., heat-treated copperpowder, heat-treated copper carbonate/copper hydroxide, chemicallytreated copper carbonate/copper hydroxide, chemically treated copperhydroxide, or malachite material) are unsupported catalysts.

A copper metal powder material can be made a useful hydrogenationcatalyst when treated as described herein. A representative copper metalpowder can be obtained from Umicore Canada (Fort Saskatchewan, Canada).Preferably, these copper powders are high-purity, non-agglomerated,spheroidal products that are also used in electronics applications, suchas termination pastes, inner electrode inks, and conductive traces. Fourgrades of copper powder can be obtained from this manufacturer: UCP 500,UCP 1000, UCP 2000, and UPC 4000. They are characterized by themanufacturer as having the following tap density (grams/cubiccentimeter), respectively: 3.6; 3.5; 3.6; and 4.8. In addition, they arecharacterized by the manufacturer as having the following surface areas(square meters/gram), respectively: 1.0; 0.8; 0.6; and 0.4 and particlesizes (microns), respectively; 0.5; 1.0; 2.0; and 4.0.

In particular, a heat-treated copper metal can be used in thehydrogenation or partial hydrogenation of an unsaturated fatty acylcompound using the process described above. Most preferably, such amaterial comprises or consists essentially of a heat treated coppermetal hydrogenation catalyst having a particle size of about 0.5microns. The heat treatment for this particular catalyst comprisesheating the copper metal powder at a temperature from about 50° C. toabout 500° C. More preferably the temperature is from about 150° C. toabout 400° C., and most preferably the temperature is from about 200° C.to about 350° C. It is also preferred that the copper powder material isheated in the presence of oxygen. Oxygen may be present during the heattreatment by allowing ambient air or more purified O₂ to contact thecopper powder material.

This catalyst is prepared by starting with a copper metal powder asdescribed above. This material is then heated as described above, andthen the material is preferably subjected to a process that produces apowder of substantially uniform consistency. The term “substantiallyuniform consistency” means a powder material that is essentially free ofagglomerated material or clumps. During the heat treatment,agglomeration or clumping of the copper powder may occur. It has beenfound that the catalytic activity of the copper metal powder is improvedif the agglomerates or clumps are disrupted to form a powder material ofsubstantially uniform consistency. A heat treated copper metal powderhydrogenation catalyst can comprise agglomerates or clumps but it ispreferred that the material is essentially free of them.

Any method of disrupting the agglomerates or clumps is envisioned.Preferably, the material is tumbled, deagglomerated, ground, stirred orslurried (with or without grinding) to disrupt the agglomerates orclumps. Preferably, after disrupting the agglomerates or clumps, thematerial can be heated again as described above and/or the material canthen be dried by vacuum, heating or any other drying method known in theart.

A copper metal powder prepared as described above is a usefulhydrogenation catalyst especially for producing hydrogenated vegetableoils as food ingredients or for food production. Using the methoddescribed herein, such copper metal hydrogenation catalysts preferablyyield hydrogenated vegetable oils containing the following ratios offatty acids: C18:2/C18:0 above about 11.0; C18:2/C18:1 no greater thanabout 2; C18:3/C18:0 no greater than about 1. The process preferablyyields a hydrogenated oil that further comprises a trans fatty acidcontent of no greater than about 8% depending on the content oflinolenic acid in the starting soybean oil.

All fatty acid ratios as described herein were derived by determiningthe fatty acid profile of starting oils and hydrogenated oil by gaschromatography (GC) according to AOCS methods. Values for C18:0 werereported directly from chromatography, values for C18:1 and C18:2 wereobtained by summing the contents of cis and trans isomers of C18:1 andC18:2 fatty acids, respectively. Reactions were monitored by refractiveindex (RI) and where fatty acid profiles are reported from this data itwas obtained by correlating these RI values to published data containingboth RI and GC data.

A copper carbonate/copper hydroxide material can be made to be a usefulhydrogenation catalyst when treated as described herein. A coppercarbonate/copper hydroxide material comprises copper carbonate andcopper hydroxide and can be described as basic copper carbonate. Basiccopper carbonate is a product of commerce and contains about 50+% coppercarbonate, with the remainder consisting essentially of copperhydroxide. A representative material can be obtained from World Metal,LLC (Sugar Land, Tex., USA). The density can range from about 500 toabout 2000 kg/cubic meter. The material is basic in character andinsoluble in water. As received from the manufacturer, the material canbe green in color. However, supplies often vary in shades of color anddensity (darker green or olive, and heavier, lighter or fluffier)reflecting variations in raw materials and manufacturing procedures.Despite variations in the physical appearance of the material, theamount of contained copper metal remains essentially constant.

A heat or chemically treated copper carbonate/copper hydroxide materialcan be used in the hydrogenation or partial hydrogenation of anunsaturated fatty acyl compound using the process described above. Sucha material comprises or consists essentially of a heat or chemicallytreated copper carbonate/copper hydroxide hydrogenation catalyst.

The heat treatment for the copper carbonate/copper hydroxidehydrogenation catalyst comprises heating a copper carbonate/copperhydroxide material as described above to a temperature of not less thanabout 100° C. until the material is black in color, and a hydrogenationcatalyst is prepared. In a preferred embodiment, the method of preparinga copper carbonate/copper hydroxide hydrogenation catalyst comprises, a)heating a copper carbonate/copper hydroxide material at a temperature nogreater than about 320° C. (e.g., at a temperature from about 100° C. toabout 320° C.), and b) heating the material of step a) at a temperatureat least about 5° C. higher than the temperature in step a). Thus, instep a) the material is heated and then in step b), the temperature isincreased such that the material is then heated at a temperature atleast about 5° C. higher than the temperature in step a). At the end ofthis process, the catalyst will be black in color.

Most preferably, the method comprises three steps, a) heating a coppercarbonate/copper hydroxide material at a temperature no greater thanabout 320° C. for a first period of time, b) disrupting anyagglomeration or clumps in the material possibly formed during heating,and c) heating the material of the prior disrupting step at atemperature at least about 5° C. higher than the temperature in step a)for a second period of time.

Preferably, the first period of time is not greater than about 30minutes, and the second period of time is a period of time sufficient toproduce a hydrogenation catalyst. Specifically, the second period oftime will be long enough to yield a catalyst that is black in color.This second period of time is preferably from about 1 minute to about 2hours. More preferably, the second period of time is from about 5minutes to about 1 hour. Most preferably, the second period of time isfrom about 10 minutes to about 25 minutes.

In any embodiment, the preparation of this catalyst can also include astep of disrupting agglomerates or clumps during the heating. Methods ofdisrupting agglomerates and clumps have been described above. Afterconducting a process of disrupting the agglomerates and clumps, it ispreferred that the material has substantially uniform consistency.

It is also preferred that the copper carbonate/copper hydroxide materialis heated in the presence of oxygen. Oxygen may be present during theheat treatment by allowing ambient air or more purified O₂ to contactthe copper powder material.

The copper carbonate/copper hydroxide hydrogenation catalyst asdescribed above is useful for producing hydrogenated vegetable oils asfood ingredients or for food production. Using the method describedherein, such copper carbonate/copper hydroxide hydrogenation catalystspreferably yield hydrogenated vegetable oils containing the followingratios of fatty acids respectively: Illustrative Oil 1) 18:2/18:0 aboveabout 11.0; 18:2/18:1 no greater than about 2.2; 18:3/18:0 no greaterthan about 1.7; and Illustrative Oil 2) 18:2/18:0 above about 11.0;18:2/18:1 no greater than about 2.2; 18:3/18:0 no greater than about 1.The above oils preferably further comprise a trans fatty acid content ofno greater than about 8%.

In another embodiment of the invention, a catalyst comprising achemically treated copper carbonate/copper hydroxide material can beused in hydrogenation or partial hydrogenation using the processdescribed above. By the term “chemically treated copper carbonate/copperhydroxide material,” it is meant that the copper carbonate/copperhydroxide material is contacted with a reagent to improve its ability tocatalyze a hydrogenation reaction.

In an embodiment, the copper carbonate/copper hydroxide material ischemically treated with a hydrogen peroxide solution. Thus, in thisembodiment, a chemically treated copper carbonate/copper hydroxide isprepared by a) preparing a mixture by contacting copper carbonate/copperhydroxide material with a hydrogen peroxide solution, wherein saidmixture is maintained at temperatures from about −5° C. to about 100°C.; and b) separating a solid material from said mixture; wherein ahydrogen peroxide treated copper carbonate/copper hydroxidehydrogenation catalyst is prepared.

The hydrogen peroxide can be in the form of an aqueous solution.Concentrations of aqueous hydrogen peroxide can range from about 1% toabout 90% hydrogen peroxide. In embodiments of the invention, theconcentration is from about 40% to about 60%, or from about 45% to about55%. In yet another embodiment, the concentration is about 50% assupplied commercially.

As mentioned above, the mixture is maintained at temperatures from about−5° C. to about 100° C. In an embodiment, the mixture is maintained attemperatures from about −5° C. to about 30° C.

The preparation of this catalyst can also include disruptingagglomerates or clumps in the material. Agglomerates or clumps in thematerial can be disrupted before and/or after the solid material isseparated from the mixture (step b, above). Methods of disruptingagglomerates and clumps are described above. In embodiments of theinvention, agglomerates or clumps in the material are disrupted bygrinding, preferably by slurry grinding in an appropriate liquid. Forexample, the material can be slurry ground in hydrogen peroxide, whichcan be the same or different from, and at the same or differentconcentration of, the hydrogen peroxide used in step a). After slurrygrinding, the material can be separated from the liquid phase by anymethod known in the art such as filtering (e.g. vacuum filtering),decanting, centrifuging, or any combination thereof. Optionally, thematerial can then be dried by vacuum, heating or other drying methodknown in the art.

In an embodiment, the hydrogen peroxide-treated copper carbonate/copperhydroxide hydrogenation catalyst may be subjected to one or moreadditional chemical treatments with a hydrogen peroxide solution. Thehydrogen peroxide-treated copper carbonate/copper hydroxidehydrogenation catalyst may be subjected to any of rinsing, filtering ordrying prior to being subjected to one or more additional chemicaltreatments with a hydrogen peroxide solution.

The copper carbonate/copper hydroxide hydrogenation catalyst asdescribed above is useful for producing hydrogenated vegetable oils asfood ingredients or for food production. Using the method describedherein, such copper carbonate/copper hydroxide hydrogenation catalystspreferably yield hydrogenated vegetable oils containing the followingratios of fatty acids: Illustrative Oil 1) C18:2/C18:0 above about 11.0;C18:2/C18:1 no greater than about 2.2; C18:3/C18:0 no greater than about1.7; Illustrative Oil 2) C18:2/C18:0 above about 12.0; C18:2/C18:1 nogreater than about 2.1; C18:3/C18:0 no greater than about 1.6;Illustrative Oil 3) C18:2/C18:0 above about 12.2; C18:2/C18:1 no greaterthan about 2.0; C18:3/C18:0 no greater than about 1.4; and IllustrativeOil 4) C18:2/C18:0 above about 11.3; C18:2/C18:1 no greater than about1.65; C18:3/C18:0 no greater than about 0.65. The above oils preferablyfurther comprise a trans fatty acid content of no greater than about 8%.

In another embodiment of the invention, a catalyst comprising orconsisting essentially of a chemically treated copper hydroxide materialcan be used in hydrogenation or partial hydrogenation using the processdescribed above. By the term “chemically treated copper hydroxidematerial,” it is meant that the copper hydroxide material is contactedwith a reagent to improve its ability to catalyze a hydrogenationreaction.

In an embodiment, the copper hydroxide material is chemically treatedwith a hydrogen peroxide solution. Thus, in this embodiment, thechemical treatment of a material comprising or consisting essentially ofa copper hydroxide material comprises, a) preparing a mixture bycontacting a copper hydroxide material with a hydrogen peroxidesolution, wherein said mixture is maintained at temperatures from about−5° C. to about 100° C.; and b) separating a solid comprising saidcatalyst, wherein a hydrogen peroxide treated copper hydroxidehydrogenation catalyst is prepared.

The hydrogen peroxide can be in the form of an aqueous solution.Concentrations of aqueous hydrogen peroxide can range from about 1% toabout 90% hydrogen peroxide. In embodiments of the invention, theconcentration is from about 40% to about 60%, or about 45% to about 55%.In yet another embodiment, the concentration is about 50% as suppliedcommercially.

The temperature(s) in step a) are preferably from about 0° C. to about100° C. The material can be separated from the liquid phase by anymethod known in the art such as filtering (e.g. vacuum filtering),decanting, centrifuging, or any combination thereof. Optionally, thematerial can then be dried by vacuum, heating or other drying methodknown in the art.

The copper hydroxide hydrogenation catalyst can also be prepared bycontacting with hydrogen peroxide as described herein, followed byseparating from the hydrogen peroxide by the methods described herein,drying by any known method in the art, and subsequently being heated inan oil at a temperature above about 50° C. Preferably, the temperatureis from about 100° C. to about 250° C. The oil can be any oil, butpreferably the oil is an edible oil such as a vegetable oil. The copperhydroxide hydrogenation catalyst can be separated from the oil if, forexample, the oil in this step is not a composition to be hydrogenated,and used to hydrogenate a composition comprising at least two sites ofunsaturation. Preferably, the catalyst is heated until the color of thecatalyst is black.

The chemically treated copper hydroxide hydrogenation catalyst asdescribed above is useful for producing hydrogenated vegetable oils asfood ingredients or for food production. Using the method describedherein, such copper hydroxide hydrogenation catalysts preferably yieldhydrogenated vegetable oils containing the following ratios of fattyacids: Illustrative Oil 1) C18:2/C18:0 above about 11.0; C18:2/C18:1 nogreater than about 1.8; C18:3/C18:0 no greater than about 1.0;Illustrative Oil 2) C18:2/C18:0 above about 11.5; C18:2/C18:1 no greaterthan about 1.7; C18:3/C18:0 no greater than about 0.55; and IllustrativeOil 3) C18:2/C18:0 above about 11.7; C18:2/C18:1 no greater than about1.69; C18:3/C18:0 no greater than about 0.53. The above oils preferablyfurther comprise a trans fatty acid content of no greater than about10%. More preferably, the above oils further comprise a trans fatty acidcontent of no greater than about 8%.

A hydrogenation catalyst comprising a malachite material can also beused in the hydrogenation or partial hydrogenation of an unsaturatedfatty acyl compound using the process described above. By “malachitematerial,” it is meant a synthetic or natural material containingmalachite. Malachite (also referred to in scientific literature ascopper (II) carbonate hydroxide, Cu₂CO₃(OH)₂, basic copper carbonate, orcopper carbonate/copper hydroxide) has CAS Registry Number 1319-53-5with the following structure:

In an embodiment of the invention, the malachite material is naturallyoccurring malachite mineral. Natural malachite can be found in theoxidations zone of polymetallic deposits in ore fields, and appear asradiate-fibrous, spheroidal, and sintered aggregates with shell-likecleavage, silky luster, and a characteristic green color in varicoloredband due to diverse grain sizes. Natural malachite can be purchased inclumps from rock collectors, and may contain trace amounts ofphosphorus, calcium, strontium, zinc and manganese.

In another embodiment of the invention, the malachite material issynthetically prepared malachite. The synthetically prepared malachitecan be prepared by any suitable method. For example, the syntheticallyprepared malachite is a precipitated malachite, i.e., malachite preparedby a precipitation method, such as by precipitation of copper cationsand carbonate anions. A suitable method of preparation of precipitatedmalachite is disclosed in H. Parekh and A. Hsu, “Preparation ofsynthetic malachite. Reaction between cupric sulfate and sodiumcarbonate solutions,” Industrial & Engineering Chemistry ProductResearch and Development 7(3): 222-6 (1968). Examples of the preparationof precipitated malachite are described in Example 9, below.

In an embodiment, the hydrogenation catalyst comprising a malachitematerial (e.g. as a naturally occurring mineral or syntheticallyprepared by precipitation) is unsupported. That is, an unsupportedcatalyst comprising a malachite material according to the presentinvention can be used for hydrogenation of an unsaturated composition,and particularly for a composition containing at least two sites ofunsaturation.

In embodiments of the invention, the malachite material can bechemically treated, i.e. contacted with a reagent to improve its abilityto catalyze a hydrogenation reaction. In an embodiment, the malachitematerial is chemically treated by contacting it with a hydrogen peroxidesolution. For example, the malachite material can be chemically treatedby a) contacting the malachite material with a hydrogen peroxidesolution to form a mixture, and maintaining the mixture at about −5° C.to about 100° C. and b) separating the treated material from themixture. The conditions for preparing the chemically treated malachite(e.g., concentration of reagent(s), temperature, and separationtechnique(s)) include those discussed for the chemically treated coppercarbonate/copper hydroxide catalyst, above.

A hydrogenation catalyst comprising a malachite material as describedabove is useful for producing hydrogenated vegetable oils as foodingredients or for food production. Such malachite materialhydrogenation catalysts (and particularly the unsupported syntheticprecipitated malachite catalyst) preferably yield hydrogenated vegetableoils containing the following ratios of fatty acids: C18:2/C18:0 aboveabout 10; C18:2/C18:1 no greater than about 1.76; C18:3/C18:0 no greaterthan about 0.61. In embodiments, the above hydrogenated oils furthercomprise a trans fatty acid content of no greater than about 8%.

Any of the catalysts of the present invention (i.e., heat-treated coppermetal, chemically and optionally heat-treated copper hydroxide, heat orchemically treated copper carbonate/copper hydroxide, and a malachitematerial) can be further treated prior to use in a hydrogenationreaction in order to improve its ability to catalyze a hydrogenationreaction. The catalysts are further treated by heating the catalysts inan oil in the presence or absence of additional hydrogen. The furthertreated catalysts are then recovered from the oil and can be used tocatalyze hydrogenation reactions as disclosed herein.

The oil that can be used in the further treatment of the catalysts ofthe invention is not particularly limited, and can include any vegetableoil, animal oil, butterfat, cocoa butter, cocoa butter substitutes,illipe fat, kokum butter, milk fat, mowrah fat, phulwara butter, salfat, shea fat, borneo tallow, lard, lanolin, beef tallow, mutton tallow,tallow, animal fat, canola oil, castor oil, coconut oil, coriander oil,corn oil, cottonseed oil, hazelnut oil, hempseed oil, jatropha oil,linseed oil, mango kernel oil, meadowfoam oil, mustard oil, neat's footoil, olive oil, palm oil, palm kernel oil, peanut oil, rapeseed oil,rice bran oil, safflower oil, sasanqua oil, shea butter, soybean oil,sunflower seed oil, tall oil, tsubaki oil, tung oil, marine oils,menhaden oil, candlefish oil, cod-liver oil, orange roughy oil, pileherd oil, sardine oil, whale oils, herring oils, triglyceride,diglyceride, monoglyceride, triolein palm olein, palm stearin, palmkernel olein, palm kernel stearin, triglycerides of medium chain fattyacids, and derivatives, conjugated derivatives, genetically-modifiedderivatives and mixtures thereof.

The temperature and time for which the catalyst/oil mixture is heated tofurther treat the catalyst is not particularly limited. In embodimentsof the invention, the temperature is from about 100° C. to about 200°C., and the time ranges from about 1 minute to about 120 minutes,typically about 15 minutes

The further treated catalysts of the invention are expected to provide alowered linolenic acid content and/or lowered trans fatty acid formationin a hydrogenation reaction compared to catalysts that are not furthertreated. Further treatment of a copper hydroxide catalyst and theresults of hydrogenation using that catalyst is illustrated in Example7, below.

The catalysts of the present invention can be reused or recycled. Thus,the catalysts described herein can be used to hydrogenate or partiallyhydrogenate subsequent compositions comprising at least two sites ofunsaturation. In one example of this embodiment, following the step ofheating a mixture comprising a catalyst and a composition comprising atleast two sites of unsaturation under a hydrogen atmosphere, the solidmaterial is separated from the mixture.

Separation of the solid material from a hydrogenated oil can beperformed by any means, such as those described above for separating asolid from a non-solid material, and at any convenient processingtemperature. Suitable methods include centrifugation, settling,decantation, filtration (e.g., vacuum filtration), contact with a filteraid, contact with a liquid or solid chelating agent, addition of anactivated adsorbent, or any combination thereof. For example, vacuumfiltration can be carried out using filter aids, such as Celite 503Diatomaceous Earth (World Minerals Inc., Goleta, Calif.). Otherseparation methods include contact with a liquid or solid chelatingagent such as citric acid solution, by addition of activated adsorbentsuch as activated SorbsilR92 (INEOS Silicas Americas, LLC, Joliet,Ill.), and filtering through a filter aid.

Subsequent to separation, the solid material can be contacted with acomposition containing at least two sites of unsaturation to form amixture, and this will then be heated at a temperature from about 50° C.to about 250° C. under a hydrogen atmosphere wherein said composition ishydrogenated. This process can be repeated such that the solid materialcomprising the hydrogenation catalyst is contacted with subsequentcompositions containing at least two sites of unsaturation and thenseparated from the hydrogenated compositions, wherein the hydrogenatedcompositions will have been hydrogenated using the methods describedherein.

EXAMPLES Example 1 Hydrogenation Using Neat Powders

Neat powders as received from various chemical supply companies weretested as hydrogenation catalysts without any pretreatment.

Hydrogenation reaction: Soybean oil (Linolenic acid 7.1%, trans fattyacid 0.2%, Conjugated linoleic acid 0.1%) was dewatered under vacuum(ca. 0.5-2 torr) at 80-85° C.; 600 grams of dewatered soybean oil werecharged into a 2 liter pressure reactor (Parr Model 4542). Catalyst(nominally 0.1% copper as a percentage of oil used in a given reaction)was added, and the vessel was sealed. The reaction mixture was heated to160° C. under a hydrogen atmosphere of 60 psi with a slight hydrogen gaspurge through a fritted disk in the bottom of the vessel. The resultsare given below in Table 1:

TABLE 1 Final Linolenic Final trans Reaction acid content fatty acidFinal CLA* Catalyst time (%) content (%) content (%) Cu(OAc)₂ NoReaction Cu(NO₃)₂ No Reaction CuCl₂ No Reaction CuS No Reaction CuSO₄ NoReaction CuO No Reaction Cu(OH)₂ 5 hours 5.8 No Data No Data *CLA:Conjugated Linoleic Acid

Copper compounds as received are shown to be ineffective hydrogenationcatalysts under the conditions described.

Example 2 Reference Hydrogenation Using Copper Chromite

A commercially available copper chromite catalyst (G22/2 in powder formfrom Sud Chemie Inc.) was used without modification. The hydrogenationreaction was identical to Example 1. The results given below in Table 2show that this catalyst produced desirable levels of linolenic acid withlow trans fat content and about 1% formation of CLA:

TABLE 2 Final Linolenic Final trans Reaction acid content fatty acidFinal CLA* Catalyst time (%) content (%) content (%) Copper 5 hours 1.747.45 0.96 chromite

Example 3 Hydrogenation Using Copper Powder

Hydrogenation reactions using commercially available copper powder(Umicore Canada Inc., product # UCP 500, particle size: 5 microns) werecarried out. The results are given in Table 3 below.

No treatment: UPC 500 (12.1 grams) was added without treatment to 598grams of dry refined and bleached soybean oil. Hydrogenation conditionswere as in Example 1.Treatment 1: UPC 500 (12.0 grams) was heated in a muffle furnace at 300°C. for several 4-5 minute intervals. After the third interval, thematerial was subjected to disrupting the agglomerates or clumps. Thehydrogenation was carried out as in Example 1.

TABLE 3 Final linolenic acid Copper Reaction C18:0 C18:1 C18:2 contentTrans powder time (hr) (%) (%) (%) (%) (%) Soybean oil 4.3 22.0 52.9 7.20.2 No treatment 7 4.3 24.3 51.7 7.0* 0.6 Treatment 1 5 4.3 31.4 49.22.4 7.8 *linolenic acid content estimated from RI (refractive index)

Copper powder as received (“No treatment” in Table 3) was ineffectiveunder hydrogenation conditions, and raised the content of undesirabletrans fatty acids without decreasing the linolenic acid levelsignificantly. After heat treatment including disrupting anyagglomerates and clumps, the catalyst produced an oil with a decrease ofC18:3 with a reasonable increase in trans fatty acids. As shown in Table3, the level of C18:1 increased, and the level of C18:0 was unchanged.

Example 4 Heat-Treated or Hydrogen Peroxide-Treated CopperCarbonate/Copper Hydroxide

Hydrogenation reactions using commercially available coppercarbonate/copper hydroxide (basic copper carbonate, CUCOCER, obtainedfrom World Metals, Inc. and Sigma Aldrich basic copper carbonate) werecarried out. The results are given in Tables 4.1 and 4.2 below.

No treatment: CUCOCER and Sigma Aldrich basic copper carbonate (6 grams)were used as received.Vacuum dried: CUCOCER was vacuum dried overnight at 350° F. (177° C.) or500° F. (260° C.) for 1 hour at 20 mm Hg.

Heat Treatment:

Treatment 1a: CUCOCER (1.05 grams) was briefly treated at 360° C. in amuffle furnace until the color turned to avocado green. Thehydrogenation reaction was carried out as in Example 1 using the entireamount as catalyst.Treatment 1b: CUCOCER (1.05 grams) was treated at 360° C. in a mufflefurnace until the color turned darker than treatment 1a, to greenishbrown (olive drab). The hydrogenation reaction was carried out as inExample 1 using the entire amount as catalyst.Treatment 1c: CUCOCER (1.05 grams) was heated in a muffle furnace at300° C. for ten minutes, followed by 350° C. for about 10 minutes. Thecatalyst color was black after this treatment. The hydrogenationreaction was carried out as in Example 1 using the entire amount ascatalyst.Treatment 1d: Sigma-Aldrich basic copper carbonate (25.0 grams) washeated at 350° C. for four minute intervals, removed from the oven andswirled briefly to mix, then returned to the muffle furnace for fourminutes of additional heating. When removed from the furnace thematerial had it turned black. The hydrogenation reaction was carried outas in Example 1 using the entire 25 grams as catalyst.

TABLE 4.1 Final Trans Linolenic fatty acid Basic copper Reaction C18:0C18:1 C18:2 acid content content carbonate time (%) (%) (%) (%) (%) Notreatment 5 hours No reaction CUCOCER and Sigma Aldrich Vacuum 4 hoursNo reaction Dried CUCOCER Treatment 1a 5 hours No reaction Treatment 1b5 hours 4.2 24.6 51.8 6.9 1.3 Treatment 1c 5 hours 4.3 31.7 48.8 2.5 8.6Treatment 1d 2 hours No reaction Sigma Aldrich

The results above show that copper carbonate/copper hydroxide asreceived was ineffective as a hydrogenation catalyst. When CUCOCER washeated at 350° C. so that the powder turned black (Treatment 1c), anexcellent hydrogenation catalyst was obtained by this process. Oilhydrogenated with this catalyst had diminished content of linolenic acidand C18:2. Additionally, the content of C18:1 increased without anynoticeable change in C18:0.

Hydrogen Peroxide Treatment:

When CUCOCER was contacted with hydrogen peroxide it darkened to a browncolor but did not turn black as when heated at 350° C.Treatment 2a: CUCOCER (4.0 grams) was slurried with 10 ml of 5% hydrogenperoxide for a few minutes. Heat was generated during the treatment, andthe CUCOCER turned an avocado green color during treatment. Thetreatment reaction was terminated by filtering treated CUCOCER through abuchner funnel followed by washing with deionized water. The chemicallytreated CUCOCER was dried in a vacuum desiccator. The hydrogenationreaction was carried out as in Example 1 using 1.05 g catalyst.Treatment 2b: CUCOCER (5.4 grams) was slurried with 10 ml of 5% hydrogenperoxide for a few minutes. Heat was generated during the treatment, andthe CUCOCER turned a dark avocado green color during treatment. Thetreatment reaction was terminated by filtering treated CUCOCER through abuchner funnel followed by washing with deionized water. The chemicallytreated CUCOCER was dried in a vacuum desiccator. The hydrogenationreaction was carried out as in Example 1 using 1.05 g catalyst.Treatment 2c: Sigma Aldrich basic copper carbonate (24.4 grams) wasslurried in 60 ml water. Aliquots (10-15 ml) of a 5% solution ofhydrogen peroxide totaling 40 ml were added to the slurry and the slurrywas allowed to incubate for 60 minutes. The slurry was filtered througha buchner funnel and washed with deionized water, then dried at roomtemperature overnight in a vacuum desiccator. The hydrogenation reactionwas carried out as in Example 1 using 1.05 g catalyst.Treatment 2d: Sigma-Aldrich basic copper carbonate (20.0 grams) wasslurried in water with a total of 10 ml of 50% H₂O₂ added in 2 mlaliquots while the slurry was held in an ice bath. The product wasfiltered, washed and dried in a desiccator as in treatment 2c. Thereaction was carried out as in Example 1 using 1.05 g catalyst exceptthat the reaction was run at 200° C.Treatment 2e: Treated Sigma-Aldrich-basic copper carbonate fromTreatment 2d (˜6 grams) was further treated by placing it in a mortarand slurry grinding with 2 ml of 50% H₂O₂; this was allowed to becontacted for 30 minutes while stirring. The catalyst was filtered anddried in a vacuum desiccator. Hydrogenation was carried out as inTreatment 2d using 1.05 g catalyst.

TABLE 4.2 Final Trans Linolenic fatty acid Basic copper Reaction C18:0C18:1 C18:2 acid content content carbonate time (%) (%) (%) (%) (%)Treatment 2a 5 hours 4.3 25.3 51.6 6.6 1.9 CUCOCER Treatment 2b* 7 hours4.3 26.4 51.8 4.3 3.6 CUCOCER Treatment 2c* 6 hours 4.2 25.7 51.4 5.52.5 Sigma Aldrich Treatment 2d 3 hours 4.3 31.3 48.6 2.8 8.1Sigma-Aldrich Treatment 2e 45 min. 4.3 30.0 49.4 2.8 6.5 Sigma-Aldrich*Fatty acids estimated from RI

CUCOCER prepared by Treatment 2a was catalytically active. CUCOCERtreated to a darker color in Treatment 2b was even more active. Thelatter yielded a desirable reduction in linolenic acid withoutsubstantially changing the other fatty acid levels. Hydrogen peroxidetreatments were very effective with Sigma Aldrich basic coppercarbonate. Treatment 2c, produced an active catalyst; however, treatment2d produced a more active catalyst. Activity was increased even furtherin Treatment 2e. The resulting catalyst produced desirable linolenicacid decrease and increased C18:1 content in a very short reaction time(45 minutes).

Example 5 Hydrogenation Using H₂O₂-Treated Copper Hydroxide

Hydrogenation reactions using commercially available copper hydroxide(CUHSULC from World Metals, Inc., also called copper (II) hydroxide)were carried out. The results are given in Table 5 below.

Hydrogen Peroxide Treatment:

Treatment 2a: CUHSULC (4.5 grams) was slurried in 10 ml of a 50%solution of hydrogen peroxide. The slurry was filtered on a Buchnerfunnel, washed with water and allowed to dry for 48 hours in a vacuumdissicator. This catalyst (0.96 grams) was added to 600 g oil and thehydrogenation reaction was carried out as in Example 1.Treatment 2b: CUHSULC (5.0 g) was slurried in an ice bath in 10 ml of a50% solution of hydrogen peroxide, followed by addition of 5 ml of 50%hydrogen peroxide. The slurry was filtered on a Buchner funnel, washedwith water and allowed to dry for 48 hours in a vacuum dissicator toform an olive drab colored powder. 1.05 Grams of this CUHSULC catalystwas added to 600 grams of RB soy oil (dry) and the hydrogenationreaction was carried out as in Example 1.Treatment 2c: CUHSULC (5.43 grams) was treated with 10 ml 50% H₂O₂ addeddropwise over an ice bath and dried in a vacuum desiccator. Thehydrogenation was done as in Example 1 using 1.05 g catalyst.Treatment 2d: CUHSULC (10.205 g) was slurried in 25 ml water, treatedwith 10 ml 50% H₂O₂ added dropwise over an ice bath and dried in avacuum desiccator. The hydrogenation was done as in Example 1 using 1.05g catalyst.

TABLE 5 Final Final trans Final Copper linolenic fatty acid CLAhydroxide Reaction C18:0 C18:1 C18:2 acid content content contenttreatment time (%) (%) (%) (%) (%) (%) None 5 hours No reaction 2a 2hours 4.3 30.5 51.0 1.9 ~7.5 0.7 2b 2 hours 4.2 32.2 49.0 1.69 9.1 0.62c 2 hours 4.3 29.9 50.4 2.3 7.3 0.8 2d 1 hour  4.3 29.9 50.0 2.2 7.30.8

Copper (II) hydroxide catalyst prepared by all variations of treatment 2were extremely effective hydrogenation catalysts and rapidly produced anoil with desirable levels of linolenic acid with low trans fat contentand little formation of CLA.

Example 6 Reuse of Copper Hydroxide Catalyst

CUHSULC (10.21 grams) was treated by first adding 25 ml of H₂O to effecta slurry, after which 10 ml 50% hydrogen peroxide was added dropwise tothe slurry in an ice bath. The treated slurry was then filtered, washedand dried in a vacuum desiccator. The hydrogenation was run using 2.108grams of catalyst according to Example 1. The RI of the oil was 1.46151after 15 minutes and 1.46140 at 30 minutes.

Second use: the catalyst was recovered by centrifuging the reactionmixture at 9000 rpm for 15 minutes. No visible catalyst remained in theoil. The oil was decanted off and fresh oil was added and used totransfer the catalyst to the reaction vessel in slurry form with minimalcatalyst loss. A total of 600 grams of oil was used for this reactionand run as in Example 1. The RI after 15 minutes was 1.46131 and after30 minutes was 1.46121, indicating a much faster initial hydrogenationthan in the first use. This example demonstrated that the catalyst isrecoverable and reusable with no observable loss of activity on thefirst reuse. The RI at one hour was 1.46112.

Third use: The catalyst was recovered again as for the second use andreused with 600 g dry RB soy oil as in Example 1. The reaction was atrace slower than the first reuse, but was still faster than the initialreaction. The RI after 30 minutes was 1.46132 (which was faster than theoriginal run, 1.46140) and 1.46121 after one hour.

Fourth use: the catalyst from the third use was recovered as in thesecond and third uses and reused a fourth time with 600 grams of dry RBsoy oil as in Example 1. The RI after 30 minutes was 1.46134 and 1.46123after one hour. The time to reach 2.5% linolenic acid for this reactionwas 2 hours. The results are given in Table 6 below.

TABLE 6 Time to attain ~2.5% linolenic Linolenic Trans Use acid acid (%)(%) 1^(st) 1 Hour 2.2 7.3 2^(nd) 1 Hour+ 2.6 7.9 3^(rd) 1 Hour+ 2.4 8.84^(th) 2 Hours 2.4 9.07

Example 7 Combined Treatments of Copper Hydroxide Catalyst

Copper hydroxide (5 g) was slurried in 10 ml of a 5% solution ofhydrogen peroxide, followed by addition of 5 ml of 50% hydrogen peroxideto the slurry in an ice bath. The slurry was filtered on a Buchnerfunnel, washed with water and allowed to dry for 48 hours in a vacuumdissicator to form an olive drab colored powder. A control reaction wasrun as in Example 1 with 1.05 grams of this catalyst. The rest of thecopper hydroxide hydrogenation catalyst was added to 30 ml soybean oiland heated to 160-170° C. with stirring until the catalyst turned black(about 15 minutes at temperature). The catalyst was recovered byfiltration and used to catalyze hydrogenation reactions as in example 1using 1.05 g catalyst at 160° and 180° C. The results are given in Table7 below.

TABLE 7 Final Final trans Copper linolenic fatty acid hydroxide ReactionC18:0 C18:1 C18:2 acid content content treatment time (%) (%) (%) (%)(%) Control 2 4.3 29.9 48.6 2.3 7.3 160° C. 160° C. 2 4.3 30.7 50.03 1.98.2 180° C. 1.5 4.3 29.3 50.3 2.6 6.6

The combination of hydrogen peroxide treatment and heating in oil in theabsence of additional hydrogen provided a hydrogen peroxide-treatedcopper hydroxide hydrogenation catalyst with excellent reduction inlinolenic acid content at short reaction times with little formation oftrans fatty acids.

Example 8 Hydrogenation Using Mineral Malachite

A sample of mineral malachite from Congo, Africa was obtained from arock collector. The mineral malachite was ground in a hand mortar in thelaboratory. After grinding the particle size distribution was: Less than10 microns, 2.1%; between 10 and 20 microns, 13.3%; greater than 20microns, 65.5%. The ground mineral malachite was used at 0.1% (wt.copper/wt. oil) to hydrogenate dried refined, bleached, deodorizedsoybean oil at 165° C. at 60 psig hydrogen for 4 hours. The resultingoil contained 5.39% C18:0, 37.82% C18:1, 41.48% C18:2, 2.92% C18:3 and16.23% trans fatty acids.

Example 9 Hydrogenation Using Precipitated Unsupported Malachite

Precipitated malachite was prepared by the following procedures, belowand used to catalyze hydrogenation reactions, as provided below.

Procedure 1: Unsupported precipitated malachite was prepared inaccordance with the description in H. Parekh and A. Hsu, “ThePreparation of Malachite. Reaction between cupric sulfate and sodiumcarbonate solutions.” Industrial & Engineering Chemistry ProductResearch and Development (1968), 7 (3), 222-6. Commercially availablebasic copper carbonate (20.04 grams, World Metal LLC, Sugar Land, Tex.)was slurried in 140 ml water, and 10.2 ml concentrated sulfuric acid wasadded to make a solution of dissolved copper sulfate. Anhydrous sodiumcarbonate (24 grams) was dissolved in 600 ml of water.

The dissolved copper sulfate solution was added to the sodium carbonatesolution over a five minute period as the sodium carbonate solution wasstirred on a stirring plate. A precipitate formed and was allowed tosettle. About 450 ml of the liquid layer was removed by decanting andanother 200 ml was removed by siphoning. The precipitate was rinsed withthree times with water (400 ml) to obtain a light green precipitate ofmalachite, which was vacuum filtered in a buchner funnel. Theprecipitated malachite was then placed in a vacuum oven at 150° C.overnight to dry.

The dried precipitated malachite was then used as an unsupportedcatalyst without further treatment to catalyze hydrogenation reactionsof refined, bleached, deodorized oil as in example 1 using 1.04 grams ofcatalyst. The results are given in Table 8 below (two different reactionconditions are illustrated).

Procedure 2: Unsupported precipitated malachite was prepared inaccordance with the description in H. Parekh and A. Hsu, “ThePreparation of Malachite. Reaction between cupric sulfate and sodiumcarbonate solutions.” Industrial & Engineering Chemistry ProductResearch and Development (1968), 7 (3), 222-6. Commercially availablebasic copper carbonate (10.15 grams, World Metal LLC, Sugar Land, Tex.)was slurried in 50 ml water, and 6.6 ml concentrated sulfuric acid wasadded to make a solution of dissolved copper sulfate. An additional 20ml of H₂O was added to resolubilize some of the CuSO₄ which hadprecipitated out of the saturated solution. Anhydrous sodium carbonate(12 grains) was dissolved in 200 ml of water.

Two-thirds of the dissolved copper sulfate solution was added dropwiseto the sodium carbonate solution as the sodium carbonate solution wasstirred on a stirring plate; the final one-third was poured in slowlyand caused significant effervescing. A precipitate formed and wasallowed to settle. Part of the liquid layer was removed by decanting andpart of the liquid layer was removed by siphoning. The precipitate wasrinsed with three times with water to obtain a light green precipitateof malachite, which was vacuum filtered in a buchner funnel. Theprecipitated malachite was then placed in a vacuum oven at 150° C.overnight to dry.

The dried precipitated malachite was then used as an unsupportedcatalyst without further treatment to catalyze hydrogenation reactionsof refined, bleached, deodorized oil as in example 1 using 1.04 grams ofcatalyst. The results are given in Table 8 below.

Procedure 3: Unsupported precipitated malachite was prepared inaccordance with the description in H. Parekh and A. Hsu, “ThePreparation of Malachite. Reaction between cupric sulfate and sodiumcarbonate solutions.” Industrial & Engineering Chemistry ProductResearch and Development (1968), 7 (3), 222-6. Commercially availablebasic copper carbonate (20.04 grams, World Metal LLC, Sugar Land, Tex.)was slurried in 140 ml water, and 10.2 ml concentrated H₂SO₄ was addedto make a solution of dissolved copper sulfate. Anhydrous sodiumcarbonate (24 grams) was dissolved in 600 ml of water.

Both solutions were heated to 60° C., and the dissolved copper sulfatesolution was added to the sodium carbonate solution over a five minuteperiod as the sodium carbonate solution was stirred on a stirring hotplate. A precipitate formed and was allowed to settle. About 450 ml ofthe liquid layer was removed by decanting and another 200 ml was removedby siphoning. The precipitate was rinsed with three times with water(400 ml) to obtain a light green precipitate of malachite, which wasvacuum filtered in a buchner funnel. The precipitated malachite was thenplaced in a vacuum oven at 150° C. overnight to dry.

The dried precipitated malachite was then used as an unsupportedcatalyst without further treatment to catalyze hydrogenation reactionsof refined, bleached, deodorized oil as in example 1 using 1.04 grams ofcatalyst. The results are given in Table 8 below.

Procedure 4: Unsupported precipitated malachite catalyst prepared byprocedure 1 was further treated with hydrogen peroxide as follows:Unsupported precipitated malachite catalyst (1 gram) was slurried inwater over ice, and 50% hydrogen peroxide (1 ml.) was added dropwiseover a 30 minute period. The slurry was allowed to warm to roomtemperature, then and vacuum filtered in a buchner funnel to provide achemically treated precipitated malachite catalyst. The chemicallytreated precipitated malachite catalyst was then placed in a vacuum ovenat 150° C. overnight to dry, then used to catalyze hydrogenationreactions of refined, bleached, deodorized oil as in example 1 using1.04 grams of catalyst. The results are given in Table 8 below.

Commercial basic copper carbonate: Commercial basic copper carbonatepreviously purchased from Mallinckrodt Laboratory Chemicals(Phillipsburg, N.J.) was tested as a catalyst without further treatmentto catalyze hydrogenation reactions of refined, bleached, deodorized oilas in Example 1 using 0.504 grams of catalyst. The results are given inTable 8 below.

TABLE 8 Final Final trans Catalyst Hydrogenation linolenic fatty acidExpt preparation temperature Reaction C18:0 C18:1 C18:2 acid contentcontent No. procedure (° C.) time (%) (%) (%) (%) (%) Starting oil 4.322.0 52.85 7.5 0.2 1 1 200 3 hrs 4.32 31.18 48.89 2.18 7.38 2 1 160 7hrs 4.6 28.64 50.45 2.8 5.9 3 2 200 1 hr 4.63 32.92 46.21 1.9 8.7 4 3160 7 hrs 4.56 30.87 48.55 2.2 8.3 5 4 200 6 hrs 4.32 33.14 47.1 1.949.98 6 Commercial 200 30 min 4.20 30.72 48.79 1.82 6.94

Very good catalysts were obtained with all procedures. The catalystprepared by procedure 2 was much faster than catalysts prepared by otherprocedures. The Mallinckrodt basic copper carbonate provided the fastestreaction, with a decrease in linolenic acid to 1.82% in 30 minutes.

Example 9 Removal of Copper Catalyst from Hydrogenation Reactions

Hydrogenation of refined bleached soybean oil was carried out usingcommercial copper hydroxide (CUHSULC, World Metal, LLC, Sugarland,Tex.). Catalyst (1.02 grams) was added to soybean oil (600 grams) andhydrogenation was carried out for seven hours. Removal of copper fromthe hydrogenated oil was carried out by vacuum filtration through a bed(70 mm diameter, 12 mm bed depth) of Celite 503 Diatomaceous Earth(World Minerals Inc., Goleta, Calif.) to obtain filtered oil containing3.47 mg copper per kg oil. The remaining copper was removed by treatingthe filtered oil with a citric acid solution and activated SorbsilR92(INEOS Silicas Americas, LLC, Joliet, Ill.;) and filtering throughCelite for a second time. Filtered oil (466 grams) was heated to 80° C.and 14 drops of 40% citric acid solution was added to the filtered oil.This mixture was stirred about 15 minutes at 80° C. Sorbsil R92 (1.86grams) was added and stirred for about 30 minutes. The mixture was againvacuum filtered through a bed of Celite 503 as described above to obtaintreated oil free from copper (detection limit: 0.1 mg/kg).

Example 10 Ratios of Fatty Acids

Ratios of fatty acids in a) starting soybean oil, and b) oil obtainedafter hydrogenating soybean oil according to the methods above(referenced below by Table No.) were calculated and are given below inTable 9.

TABLE 9 C18:2/ C18:2C/ Linolenic/ Description # C18:0 18:1 C18:0Starting oil 12.09 2.18 1.81 Table 2 Copper chromite 15 10.94 1.85 0.53Table 2 Copper chromite 16 12.05 1.87 0.86 Table 3 Copper powder Notreat. 17 12.02 2.13 1.63 Table 3 Copper powder Treat. 1 18 11.44 1.570.56 Table 4.1 Treat. 1b World Metals 19 12.33 2.11 1.64 Table 4.1Treat. 1c World Metals 20 11.35 1.54 0.58 Table 4.2 Treat. 2a WorldMetals 21 12.00 2.04 1.53 Table 4.2 Treat. 2b World Metals 22 12.05 1.961.00 Table 4.2 Treat. 2c Sigma Aldrich 23 12.24 2.00 1.31 Table 4.2Treat. 2d Sigma-Aldrich 24 11.30 1.55 0.65 Table 4.2 Treat. 2eSigma-Aldrich 25 11.49 1.65 0.65 Table 5 2a 26 11.86 1.67 0.44 Table 52b 27 11.67 1.52 0.40 Table 5 2c 28 11.72 1.69 0.53 Table 5 2d 29 11.631.67 0.51 Table 7 Control 30 11.30 1.63 0.53 Table 7 160° C. 31 11.631.63 0.44 Table 7 180° C. 32 11.70 1.72 0.60 Example 8 Mineral malachite33 7.70 1.10 3.01 Table 8 Expt. 1 34 11.32 1.57 0.50 Table 8 Expt. 2 3510.97 1.76 0.61 Table 8 Expt. 3 36 9.98 1.40 0.41 Table 8 Expt. 4 3710.65 1.57 0.48 Table 8 Expt. 5 38 10.90 1.42 0.45 Table 8 Expt. 6 3911.62 1.59 0.43

Desired fatty acid profiles include those with reduced content oflinolenic acid without higher levels of trans fatty acids compared tothe starting oil. It is also highly desirable to carry out this reactionwithout reducing the content of C18:2 or C18:1 fatty acids, orincreasing the content of C18:0 fatty acids.

Illustratively, vegetable oils that are hydrogenated using the processesaccording to the present invention can be comprised of fatty acid chainshaving one of the following profiles:

C18:2/C18:0 ratio above about 11.0; C18:2/C18:1 ratio no greater thanabout 2.2; C18:3/18:0 ratio no greater than about 1.7;

C18:2/18:0 above about 11.3; C18:2/C18:1 no greater than about 1.65;C18:3/18:0 no greater than about 0.65;

C18:2/18:0 above about 9.95; C18:2/C18:1 no greater than about 1.80;C18:3/18:0 no greater than about 0.65; and

C18:2/18:0 above about 11.3; C18:2/C18:1 no greater than about 1.70;C18:3/18:0 no greater than about 0.65.

Having now fully described this invention, it will be understood tothose of ordinary skill in the art that the same can be performed withina wide and equivalent range of conditions, formulations, and otherparameters without affecting the scope of the invention or anyembodiment thereof.

All documents, e.g., scientific publications, patents, patentapplications and patent publications, if cited herein are herebyincorporated by reference in their entirety to the same extent as ifeach individual document was specifically and individually indicated tobe incorporated by reference in its entirety. Where the document citedonly provides the first page of the document, the entire document isintended, including the remaining pages of the document.

1-15. (canceled)
 16. A process of preparing a hydrogenation catalystcomprising: (a) preparing a mixture by contacting coppercarbonate/copper hydroxide material with a hydrogen peroxide solution,wherein said mixture is maintained at temperatures from about −5° C. toabout 100° C.; and (b) separating a solid material from said mixture;wherein a hydrogen peroxide-treated copper carbonate/copper hydroxidehydrogenation catalyst is prepared.
 17. The process of claim 16, whereinsaid hydrogen peroxide solution is about 1% to 90% hydrogen peroxide.18. The process of claim 17, wherein said hydrogen peroxide solution isabout 40% to 60% hydrogen peroxide.
 19. The process of claim 16, whereinsaid mixture is maintained at temperatures from about −5° C. to about30° C.
 20. The process of claim 16, wherein separating said solidmaterial from said mixture comprises centrifugation, settling,decantation, filtration, or any combination thereof.
 21. The process ofclaim 16, further comprising slurry grinding the solid material of step(b) with a hydrogen peroxide solution.
 22. A hydrogenation catalyst madeby the process of claim
 16. 23. The catalyst of claim 22, wherein thecatalyst is unsupported. 24-38. (canceled)
 39. A process of preparing ahydrogenation catalyst comprising: (a) preparing a mixture by contactinga copper hydroxide material with a hydrogen peroxide solution, whereinsaid mixture is maintained at temperatures from about −5° C. to about100° C.; and (b) separating a solid comprising said catalyst, wherein ahydrogen peroxide-treated copper hydroxide hydrogenation catalyst isprepared.
 40. The process of claim 39, wherein said hydrogen peroxidesolution is about 1% to about 90% hydrogen peroxide.
 41. The process ofclaim 39, wherein said temperatures in step a) are from about −5° C. toabout 30° C.
 42. The process of claim 39, further comprising heating thehydrogen peroxide-treated copper hydroxide hydrogenation catalyst in anoil in the absence of additional hydrogen.
 43. A process of preparing ahydrogenation catalyst comprising heating a copper carbonate/copperhydroxide material at a temperature of not less than about 100° C. untilsaid material is black in color, wherein a heat treated coppercarbonate/copper hydroxide hydrogenation catalyst is prepared.
 44. Theprocess of claim 43, comprising: (a) heating a copper carbonate/copperhydroxide material at a temperature from about 100° C. to about 320° C.,and (b) heating the material of step a) at a temperature at least about5° C. higher than the temperature in step a).
 45. A process of preparinga hydrogenation catalyst comprising: (a) heating a copper metal powdermaterial at a temperature from about 50° C. to about 500° C.; and (b)subjecting said copper powder from step a) to a process that disruptsagglomerates and clumps, wherein a heat-treated copper powderhydrogenation catalyst is prepared.
 46. The process of claim 45, whereinsaid copper powder has an average particle size of about 0.5 micron. 47.The process of claim 45, further comprising: c) subjecting the productof step b) to a vacuum and/or drying step.
 48. The process of claim 45,further comprising: c) heating the product of step b) at a temperaturefrom about 50° C. to about 500° C.